JP2800807B2 - Water repellent / soil repellent composition, water repellent / soil repellent substrate, and method of treating the composition - Google Patents
Water repellent / soil repellent composition, water repellent / soil repellent substrate, and method of treating the compositionInfo
- Publication number
- JP2800807B2 JP2800807B2 JP8294108A JP29410896A JP2800807B2 JP 2800807 B2 JP2800807 B2 JP 2800807B2 JP 8294108 A JP8294108 A JP 8294108A JP 29410896 A JP29410896 A JP 29410896A JP 2800807 B2 JP2800807 B2 JP 2800807B2
- Authority
- JP
- Japan
- Prior art keywords
- repellent
- composition
- water
- organic group
- independently
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 31
- 239000005871 repellent Substances 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 26
- 239000000758 substrate Substances 0.000 title description 16
- 230000002940 repellent Effects 0.000 title description 5
- 239000002689 soil Substances 0.000 title 2
- 125000000962 organic group Chemical group 0.000 claims description 19
- 230000003373 anti-fouling effect Effects 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、撥水性、防汚性に
優れた被膜を与える組成物に関するものであり、ガラ
ス、プラスチックをはじめ各種の基材に適用が可能な技
術に関する。この発明により各種基材の広い範囲での応
用展開が可能となる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for providing a film having excellent water repellency and antifouling property, and to a technique applicable to various substrates such as glass and plastic. According to the present invention, various base materials can be applied to a wide range of applications.
【０００２】[0002]
【従来の技術】各種基材、特に透明基材はその表面が人
の目に直接触れる使用状態が多い。表面へのほこり、油
汚れ等の吸着、または、表面での水の悪影響により材料
の透明感が失われることがよくある。そのため、透明基
材における撥水性または防汚性の向上の要求は多い。2. Description of the Related Art In many cases, various substrates, especially transparent substrates, are used in such a manner that the surface thereof is directly in contact with human eyes. The transparency of the material is often lost due to the adsorption of dust and oil stains on the surface, or the adverse effect of water on the surface. Therefore, there are many demands for improving the water repellency or antifouling property of the transparent substrate.
【０００３】プラスチックまたはガラスなどの製品寿
命、外観は、しばしば直接水の濡らす作用または、水に
伴われる異物粒子によって有害な影響を受けて劣化す
る。この種の悪影響には外観の損傷、汚れ、着色、腐
食、電気的特性の変化、光沢の損失などがある。これら
の問題を解決するためにいくつかの提案がなされてい
る。Product life and appearance, such as plastic or glass, are often degraded by direct water wetting or detrimentally affected by foreign particles associated with the water. Such adverse effects include damage to appearance, dirt, color, corrosion, changes in electrical properties, loss of gloss, and the like. Several proposals have been made to solve these problems.
【０００４】しかし、現在入手可能な材料では種々の理
由で不満足である。すなわち、効果の持続性、溶剤およ
び洗浄剤に対する耐性を欠く等の欠点を有していた。ま
た、耐擦傷性が低く、ガラスなどに処理した場合にその
表面がかえって傷付きやすくなる欠点も有していた（特
公昭５０−１５４７３など）。However, currently available materials are unsatisfactory for various reasons. That is, it has drawbacks such as lack of durability of the effect and resistance to solvents and cleaning agents. In addition, they have low abrasion resistance, and have the disadvantage that when they are treated with glass or the like, their surfaces are more likely to be damaged (for example, Japanese Patent Publication No. 50-15473).
【０００５】また、一般的にはこの種の組成物は塗布後
に焼成が必要な場合が多く、工程的に困難な場合があっ
たり、コスト的にも不利であった。また、何よりもこれ
らの材料より得られる撥水性、防汚性では満足できず、
使用可能な分野が限定されていた。In general, this type of composition often requires baking after coating, which may be difficult in the process or disadvantageous in cost. Also, above all, the water repellency and antifouling properties obtained from these materials are not satisfactory,
The available fields were limited.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は以上に
記述した従来の材料が有していた欠点の解消に努め、多
種類の基材に対して優れた撥水性および防汚性を付与可
能な組成物を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the conventional materials and to impart excellent water repellency and antifouling properties to various kinds of substrates. It is to provide a possible composition.
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明は、下
記式（Ａ）で表される化合物、下記式（Ｂ）で表される
化合物、および溶剤を含有する組成物であり、式（Ａ）
で表される化合物および式（Ｂ）で表される化合物の合
計量が組成物全量に対して０．１〜３０重量％であるこ
とを特徴とする撥水防汚性組成物、および該撥水防汚性
組成物を基材表面に処理し乾燥させて得られる撥水防汚
性基材、および該撥水防汚性組成物の処理方法を提供す
る。That SUMMARY OF THE INVENTION The present invention is a compound represented by the following formula (A), a compound represented by the following formula (B), and a composition containing a solvent, wherein (A )
And a compound represented by the formula (B)
The measurement should be 0.1 to 30% by weight based on the total weight of the composition.
And a water-repellent and antifouling composition characterized by the following:
Water repellent and stain resistant obtained by treating and drying the composition on the substrate surface
And a method for treating the water-repellent and antifouling composition .
【０００８】[0008]
【化２】 Embedded image
【０００９】 Ｒｆ1 ：エーテル性の酸素原子を含んでいてもよいパー
フルオロアルキル基、を含有する有機基を示す。 Ｒ1 ：水素原子または炭素数１〜１６の有機基を示す。 ａ：１または２。 ｂ：０または１。ただし、１≦ａ＋ｂ≦２である。[0009] Rf 1: an organic group containing a good perfluoroalkyl group, optionally containing an ether oxygen atom. R 1: represents a hydrogen atom or an organic group having 1 to 16 carbon atoms. a: 1 or 2. b: 0 or 1. However, 1 ≦ a + b ≦ 2.
【００１０】 Ｒｆ2 、Ｒｆ3 ：独立に、エーテル性の酸素原子を含ん
でいてもよいパーフルオロアルキル基、を含有する有機
基を示す。 Ｒ2 、Ｒ3 ：独立に、水素原子または炭素数１〜１６の
有機基を示す。 ｃ、ｄ：独立に、０、１または２であって０≦ｃ＋ｄ≦
２である。 ｅ、ｇ：独立に、０、１または２であって０≦ｅ＋ｇ≦
２である。 Ｙ：２価の有機基（ただし、ｃ＋ｅ＝０の場合には、エ
ーテル性の酸素原子を含んでいてもよいパーフルオロア
ルキレン基、を含有する２価の有機基）を示す。Rf 2 and Rf 3 each independently represent an organic group containing a perfluoroalkyl group which may contain an etheric oxygen atom. R 2 and R 3 independently represent a hydrogen atom or an organic group having 1 to 16 carbon atoms. c, d: independently , 0 , 1 or 2 and 0 ≦ c + d ≦
2. e, g: independently 0 , 1 or 2 and 0 ≦ e + g ≦
2. Y: a divalent organic group (however, in the case of c + e = 0, a divalent organic group containing a perfluoroalkylene group which may contain an etheric oxygen atom).
【００１１】以下、構成要素について詳細に記述する。
本発明の組成物において式（Ａ）で表される化合物は防
汚性、撥水性を発現するのに必須な成分である。以下、
式（Ａ）で表される化合物を（Ａ）成分という。他の化
合物においても同様に記す。 （Ａ）成分としては、例えば以下の化合物がある。ただ
し、RF’は炭素数１〜１６のパーフルオロアルキル基、
Ｒは置換または非置換の１価の炭化水素基、ｍは１以上
の整数である。Hereinafter, the components will be described in detail.
In the composition of the present invention, the compound represented by the formula (A) is an essential component for exhibiting antifouling property and water repellency. Less than,
The compound represented by the formula (A) is referred to as a component (A). Other transformation
The same applies to compounds. Examples of the component (A) include the following compounds. However, RF 'is a perfluoroalkyl group having 1 to 16 carbon atoms ,
R is a substituted or unsubstituted monovalent hydrocarbon group, m is 1 or more
Is an integer .
【００１２】[0012]
【化３】 Embedded image
【００１３】本発明の組成物には、（Ａ）成分とともに
（Ｂ）成分が含有されている。 [0013] The composition of the present invention is added together with the component (A).
The component (B) is contained.
【００１４】[0014]
【化４】 Embedded image
【００１５】 Ｒｆ2 、Ｒｆ3 ：独立に、エーテル性の酸素原子を含ん
でいてもよいパーフルオロアルキル基、を含有する有機
基を示す。 Ｒ2 、Ｒ3 ：独立に、水素原子または炭素数１〜１６の
有機基を示す。 ｃ、ｄ：独立に、０、１または２であって０≦ｃ＋ｄ≦
２である。 ｅ、ｇ：独立に、０、１または２であって０≦ｅ＋ｇ≦
２である。 Ｙ：２価の有機基（ただし、ｃ＋ｅ＝０の場合には、エ
ーテル性の酸素原子を含んでいてもよいパーフルオロア
ルキレン基、を含有する２価の有機基）を示す。Rf 2 and Rf 3 each independently represent an organic group containing a perfluoroalkyl group which may contain an etheric oxygen atom. R 2 and R 3 independently represent a hydrogen atom or an organic group having 1 to 16 carbon atoms. c, d: independently , 0 , 1 or 2 and 0 ≦ c + d ≦
2. e, g: independently 0 , 1 or 2 and 0 ≦ e + g ≦
2. Y: a divalent organic group (however, in the case of c + e = 0, a divalent organic group containing a perfluoroalkylene group which may contain an etheric oxygen atom).
【００１６】（Ｂ）成分としては、例えば以下の化合物
がある。ただし、ｎは１〜１６の整数、Ｒは置換または
非置換の１価の炭化水素基、RFはC 2 H 4 CF 3 、C 2 H 4 (CF 2 ) n
CF 3 、C 2 H 4 OCOCF 3 等の、パーフルオロアルキル基含有の
有機基である。As the component (B), for example, the following compounds
There is. Wherein n is an integer of 1 to 16, R is substituted or
Unsubstituted monovalent hydrocarbon group, RF is C 2 H 4 CF 3 , C 2 H 4 (CF 2 ) n
CF 3 , C 2 H 4 OCOCF 3 and other perfluoroalkyl group-containing
Organic group .
【００１７】[0017]
【化５】 Embedded image
【００１８】[0018]
【化６】 Embedded image
【００１９】[0019]
【化７】 Embedded image
【００２０】[0020]
【化８】 Embedded image
【００２１】[0021]
【化９】 Embedded image
【００２２】[0022]
【化１０】 Embedded image
【００２３】[0023]
【化１１】 Embedded image
【００２４】[0024]
【化１２】 Embedded image
【００２５】（Ａ）および（Ｂ）成分の添加量は、組成
物全量に対するそれらの合計量が０．１〜３０重量％と
なる量である。The amounts of the components (A) and (B)
When the total amount of them is 0.1 to 30% by weight based on the total
The amount Der made Ru.
【００２６】（Ａ）、（Ｂ）成分に目的に応じて他の成
分、添加剤を加えることは一向に支障なく、他の成分、
添加剤を加えることでこの組成物の適用範囲が大きくひ
ろがる。 Addition of other components and additives to the components (A) and (B) according to the purpose does not impede any problem.
Scope of the composition by the addition of additives is that Okikuhi <br/> filtration.
【００２７】他の成分、添加剤としては以下のようなも
のが考えられる。処理効果の耐久性、持続性を高めるた
めに下記式（Ｃ）で示される化合物がある。ただし、Ｒ
3 、Ｒ4 は独立に水素原子または炭素数１〜１６の有機
基等である。ｈ、ｉは、独立に０、１、または２であっ
て、０≦ｈ＋ｉ≦３を満たす。 The following can be considered as other components and additives. There is a compound represented by the following formula (C) for increasing the durability and durability of the treatment effect. Where R
3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 16 carbon atoms. h and i are independently 0, 1, or 2
Thus, 0 ≦ h + i ≦ 3 is satisfied.
【００２８】[0028]
【化１３】 Embedded image
【００２９】（Ｃ）成分としては、例えば以下の化合物
が挙げられる。Examples of the component (C) include the following compounds.
【００３０】[0030]
【化１４】 Embedded image
【００３１】[0031]
【化１５】 Embedded image
【００３２】その他に各種金属酸化物の超微粒子、各種
樹脂なども添加できる。また、処理性（作業性）を高め
るために界面活性剤を使用することもできる。In addition, ultrafine particles of various metal oxides, various resins and the like can be added. In addition, a surfactant can be used to enhance the processability (workability).
【００３３】上記の成分は溶剤によって希釈して使用す
る。経済性、組成物の安定性を考慮すると（Ａ）成分と
（Ｂ）成分との合計量は、組成物の全重量に対して０．
１〜３０重量％である。希釈剤としては各種溶剤が使用
できるが反応性−ＯＨ基を有しているものは（Ａ）、
（Ｂ）成分が有するイソシアネート基と反応するため液
の安定性等の理由から望ましくない。[0033] The above components Ru <br/> be used by diluting with a solvent. Considering the economic efficiency and the stability of the composition, the component (A)
The total amount with the component (B) is 0.1% based on the total weight of the composition .
1 to 30% by weight . Various solvents can be used as the diluent, but those having a reactive -OH group are (A)
It reacts with the isocyanate group of the component (B), which is not desirable for reasons such as stability of the liquid.
【００３４】処理にあたっては特別な前処理は必要ない
が、目的に応じて行うことは支障ない。フッ酸、塩酸等
による酸処理、水酸化ナトリウム、水酸化カリウム等に
よるアルカリ処理、プラズマ処理等による放電処理を行
うことは可能である。処理方法についても特に限定要素
はなく、目的に応じて選択すればよい。Although no special pre-processing is required for the processing, it does not hinder that the processing is performed according to the purpose. It is possible to perform an acid treatment with hydrofluoric acid, hydrochloric acid, or the like, an alkali treatment with sodium hydroxide, potassium hydroxide, or the like, or a discharge treatment such as a plasma treatment. The processing method is not particularly limited, and may be selected according to the purpose.
【００３５】浸漬塗布、回転塗布、スプレー塗布、流し
塗り、ローラー塗布等が適用できる。また、本発明の組
成物を各種基材に塗布し、常温で乾燥すれば優れた撥水
性および防汚性を発現するが、さらに基材へ強固に付着
させるために焼成してもよい。焼成する場合は基材の耐
熱性を考慮して５０℃〜５００℃の温度で５分〜１２０
分焼成すれば優れた処理効果が期待できる。Dip coating, spin coating, spray coating, flow coating, roller coating and the like can be applied. When the composition of the present invention is applied to various substrates and dried at room temperature, excellent water repellency and antifouling properties are exhibited. However, the composition may be baked to firmly adhere to the substrate. When sintering, at a temperature of 50 ° C to 500 ° C for 5 minutes to 120 in consideration of the heat resistance of the base material.
An excellent treatment effect can be expected if baking is performed separately.
【００３６】組成、溶剤、全重量に対する組成物の重量
比、塗布条件、焼成条件等により処理層の厚さは制御可
能であって、目的に応じて制御すればよい。例えば、本
発明の組成物はフッ素含有の成分であるため屈折率が低
い。したがって、低反射性も発現可能であり、この効果
も期待するのであれば、処理層の厚さを光学的干渉が生
じる厚さに制御すればよい。また、防汚性、撥水性を発
現するには理論的には処理層の厚さが単分子層以上あれ
ばよいので、これに経済的効果も加味して処理層の厚さ
は２μｍ以下が望ましい。さらに、本発明の組成物が含
有するフッ素成分により表面での摩擦が低減化され基材
表面での耐擦傷性に関しても著しく向上することが期待
できる。The thickness of the treated layer can be controlled by the composition, the solvent, the weight ratio of the composition to the total weight, the coating conditions, the firing conditions, and the like, and may be controlled according to the purpose. For example, the composition of the present invention has a low refractive index because it is a fluorine- containing component. Therefore, low reflectivity can be exhibited, and if this effect is expected, the thickness of the treatment layer may be controlled to a thickness at which optical interference occurs. Further, antifouling properties, the thickness of the treated layer in theory to water repellency is sufficient if more than a monolayer, the thickness of the treated layer thereto in consideration economical effects
Is preferably 2 μm or less. Furthermore, it can be expected that the friction on the surface is reduced by the fluorine component contained in the composition of the present invention, and the scratch resistance on the surface of the substrate is significantly improved.
【００３７】[0037]
【実施例】以下に本発明を実施例により具体的に説明す
るが本発明はこれらの実施例に限定されない。なお、以
下において、例１〜７および１０〜２１は本発明の実施
例であり、例８および９は参考例である。また、実施例
において用いた成形体の評価方法については次のとおり
である。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Note that
Below, Examples 1-7 and 10-21 illustrate the practice of the present invention.
These are examples, and Examples 8 and 9 are reference examples. The method for evaluating the molded body used in the examples is as follows.
【００３８】（１）防汚性の効果の確認（１−１） ヘキサデカン（Ｃ16Ｈ34）の接触角を測定し
た。(1) Confirmation of antifouling effect (1-1 ) The contact angle of hexadecane (C 16 H 34 ) was measured.
【００３９】（１−２）手の指紋を処理表面に付着後、
綿布で２０往復拭き取りその後の外観 を検査し、以下の基準で評価した。 Ａ．完全にきれいに油汚れが拭き取れる、 Ｂ．すこし油汚れが残る、 Ｃ．かなり油汚れが残る。 (1-2) After the fingerprint of the hand is attached to the processing surface,
After wiping with a cotton cloth for 20 round trips, the appearance was inspected and evaluated according to the following criteria. A. Oil dirt can be completely wiped off, B. C. A little oil stain remains. Significant oil stains remain.
【００４０】（２）撥水性の効果の確認（２−１） 水の接触角を測定した。（２−２） サンプルから２０ｃｍの距離に保持したノズ
ルから水道水をスプレーして試験した。適当な時間、水
のスプレーをテストサンプルの処理全面に当てた後スプ
レーを止め、サンプルに残った水滴を肉眼で検査し以下
の評価基準で判断した。 Ａ．サンプル表面に全く水滴が残らない、 Ｂ．サンプル表面に少し水滴が残る、 Ｃ．サンプル表面にかなり水滴が残る、 Ｄ．サンプル表面で水が濡れ広がる。[0040] (2) to measure the contact angle of confirmation (2-1) water of the effects of water repellency. (2-2) The test was performed by spraying tap water from a nozzle held at a distance of 20 cm from the sample. After spraying water on the entire surface of the test sample for an appropriate time, the spray was stopped, and water droplets remaining on the sample were visually inspected and judged according to the following evaluation criteria. A. No water droplets remain on the sample surface, B. B. Some water droplets remain on the sample surface. D. A considerable amount of water remains on the sample surface. Water spreads on the sample surface.
【００４１】（３）耐久性の評価 湿度９０％、温度５０℃の加速試験機にサンプルを入
れ、１か月放置した後、防汚性、撥水性の効果の確認を
行った。[0041] (3) Evaluation of Durability humidity of 90% Samples were placed on accelerated test machine temperature 50 ° C., after standing one month, antifouling properties, to confirm the effect of water repellency was performed.
【００４２】また、以下の例において用いたＡ１〜Ｃ４
の各成分は次の化合物である。Further, A1 to C4 used in the following examples
Are the following compounds.
【００４３】[0043]
【化１６】 Embedded image
【００４４】（例１、比較例１） Ａ１成分を１０．０ｇ、Ｂ１成分を１０．０ｇ、撹拌子
がセットされた３ツ口フラスコに混合した。さらにトル
エン１９８０ｇ加えた。以上のようにして得られた組成
物に、あらかじめ洗浄したガラス板（１０ｃｍ×１０ｃ
ｍ、厚さ５ｍｍ）を浸漬後、６ｃｍ／分の速さで引き上
げ、透明成形体を得た。以上のようにして得られた透明
成形体を評価した結果を表１に示す。また、比較例とし
て、未処理のガラスを評価した。Example 1, Comparative Example 1 10.0 g of the A1 component and 10.0 g of the B1 component were mixed in a three-necked flask equipped with a stirrer. Further, 1980 g of toluene was added. The composition obtained as described above was added to a glass plate (10 cm × 10 c
m, thickness 5 mm), and then dipped at a speed of 6 cm / min to obtain a transparent molded body. Table 1 shows the results of evaluating the transparent molded body obtained as described above. As a comparative example, an untreated glass was evaluated.
【００４５】（例２） 例１においてＢ１成分１０．０ｇのかわりにＢ２成分１
０．０ｇを用いた他は同様に行った。結果を表１に示し
た。Example 2 In Example 1, B2 component 1 was used instead of 10.0 g of B1 component.
The same procedure was performed except that 0.0 g was used. The results are shown in Table 1.
【００４６】（例３） 例１においてＡ１成分１０．０ｇのかわりにＡ２成分１
０．０ｇを用いた他は同様に行った。結果を表１に示し
た。Example 3 In Example 1, A2 component 1 was used instead of 10.0 g of the A1 component.
The same procedure was performed except that 0.0 g was used. The results are shown in Table 1.
【００４７】[0047]
【表１】 [Table 1]
【００４８】（例４〜１０、比較例２〜３） 表２に示した種類の化合物および量だけ用いて組成物を
調合し、他は例１と同様の方法で透明成形体を得た。評
価結果を表３に示した。(Examples 4 to 10, Comparative Examples 2 to 3) A composition was prepared using the compounds of the types shown in Table 2 and the amounts thereof, and a transparent molded article was obtained in the same manner as in Example 1 except for the above. Table 3 shows the evaluation results.
【００４９】[0049]
【表２】 [Table 2]
【００５０】[0050]
【表３】 [Table 3]
【００５１】（例１０） 例１で得られた透明成形体を表４に示す薬品に２４時間
浸漬した。浸漬後、洗浄を行い撥水性および撥油性の効
果について確認した。結果を表４に示した。[0051] (e.g. 10) Toru Meisei form obtained in Example 1 was immersed for 24 hours in chemicals shown in Table 4. After immersion, washing was performed to confirm the effects of water repellency and oil repellency. The results are shown in Table 4.
【００５２】[0052]
【表４】 [Table 4]
【００５３】（例１１） 例１で得られた透明成形体を、テーバー摩耗試験機にか
け、表５に示した回転数摩耗後のヘーズ値変化と防汚性
および撥水性の効果を確認した。(Example 11) The transparent molded article obtained in Example 1 was subjected to a Taber abrasion tester, and the change in haze after rotation speed wear and the effects of stain resistance and water repellency shown in Table 5 were confirmed.
【００５４】[0054]
【表５】 [Table 5]
【００５５】（例１２〜１４） 例１において基材をガラスではなくアクリル板、ポリカ
ーボネート板、ＣＲ３９板を用いた他は同様に行い、表
６に示す結果を得た。[0055] (Examples 12 to 14) Example 1 Acrylic plate rather than a glass substrate in a polycarbonate plate, another is performed in the same manner using CR39 plate to obtain shown to result in Table 6.
【００５６】（比較例４〜６） 例１２における比較例として無処理のアクリル板、ポリ
カーボネート板、ＣＲ３９板についても同様の評価を行
い、表６に示した。[0056] (Comparative Example 4-6) acrylic plate untreated as a comparative example in Example 12, a polycarbonate plate, the same also evaluated CR39 plate, shown in Table 6.
【００５７】[0057]
【表６】 [Table 6]
【００５８】（例１５） 例１において用いたガラス基材をあらかじめ２％ＨＦ水
溶液で１分前処理したガラス基材を用いた他は同様に行
い表７に示す結果を得た。(Example 15) A glass substrate used in Example 1 was pretreated with a 2% aqueous HF solution for 1 minute in the same manner except that the glass substrate was used, and the results shown in Table 7 were obtained.
【００５９】[0059]
【表７】 [Table 7]
【００６０】（例１６、比較例７） 例１と同様にして得られたガラス板の表面摩擦係数を測
定した。また、表面の耐擦傷性を評価し、未処理のガラ
ス板と比較した。耐擦傷性の評価については以下のよう
に行った。(Example 16, Comparative Example 7) The surface friction coefficient of the glass plate obtained in the same manner as in Example 1 was measured. In addition, the scratch resistance of the surface was evaluated and compared with an untreated glass plate. The evaluation of scratch resistance was performed as follows.
【００６１】表面をＳＷ（ボンスター社製＃００００）
で擦り、傷の程度を肉眼で観察した。肉眼での観察基準
は以下の通りである。 Ａ．全く傷が見られない。 Ｂ．少し傷が認められる。 Ｃ．かなり激しく傷が付く。 上記の評価結果を表８に示す。The surface is SW (# 0000 manufactured by Bonstar)
And the extent of the damage was visually observed. The observation criteria with the naked eye are as follows. A. No scratches are seen. B. Some scratches are observed. C. Scratches quite severely. Table 8 shows the evaluation results.
【００６２】[0062]
【表８】 [Table 8]
【００６３】（例１７〜２０） 例１においてコート液を塗布後、５０、１００、２０
０、４００℃で焼成した他は例１と同様にして行った。
評価結果を表９に示す。 例１７： ５０℃、 例１８： １００℃、 例１９： ２００℃、 例２０： ４００℃。(Examples 17 to 20) After the coating liquid was applied in Example 1, 50, 100, 20
The procedure was the same as in Example 1, except that calcination was carried out at 0 and 400 ° C.
Table 9 shows the evaluation results. Example 17: 50 ° C., Example 18: 100 ° C., Example 19: 200 ° C., Example 20: 400 ° C.
【００６４】[0064]
【表９】 [Table 9]
【００６５】（例２１） 例１において基材をガラスではなくアルミニウム板を用
いた他は同様に行い、表１０に示すような結果を得た。Example 21 The same procedure as in Example 1 was carried out except that an aluminum plate was used instead of glass as a base material, and the results shown in Table 10 were obtained.
【００６６】（比較例８） 例２１における比較例として無処理のアルミニウム板に
ついても同様の評価を行い、表１０に示した。Comparative Example 8 As a comparative example in Example 21, the same evaluation was performed on an untreated aluminum plate, and the results are shown in Table 10.
【００６７】[0067]
【表１０】 [Table 10]
【００６８】（比較例９） 例１において、Ｂ１成分を(CH3O)3SiC2H4C8F16C2H4Si(O
CH3)3 、Ａ１成分をC9F19C2H4Si(OCH3)3にする他は同様
に行った。結果を表１１に示した。Comparative Example 9 In Example 1, the component B1 was replaced with (CH 3 O) 3 SiC 2 H 4 C 8 F 16 C 2 H 4 Si (O
CH 3 ) 3 , except that A1 component is C 9 F 19 C 2 H 4 Si (OCH 3 ) 3
It was Tsu line to. The results are shown in Table 11.
【００６９】[0069]
【表１１】 [Table 11]
【００７０】[0070]
【発明の効果】このように本発明により得られる組成物
を基材に塗布した場合、以下のような特徴を有する。 １）常温塗布で優れた撥水性、防汚性を有する。 ２）優れた耐薬品性を有し、さらに撥水性、防汚性の効
果の持続性があり、半永久的にその状態が維持可能とな
る。 ３）広範囲の基材に対して特殊な前処理の必要がなく、
連続的に処理が可能であるため経済的効果も高い。 ４）基材表面の摩擦が低減化され、従来に無い優れた耐
擦傷性を有する。As described above, when the composition obtained by the present invention is applied to a substrate, it has the following characteristics. 1) It has excellent water repellency and antifouling properties when applied at room temperature. 2) It has excellent chemical resistance, and has a long-lasting effect of water repellency and antifouling properties, and can be maintained semipermanently. 3) No special pretreatment is required for a wide range of substrates.
Since the treatment can be performed continuously, the economic effect is high. 4) The friction on the surface of the base material is reduced, and it has an excellent scratch resistance that has never been seen before.
【００７１】以上のような特徴を有するため各種基材に
本発明の組成物を適用すれば従来では使用不可能あった
領域に適用可能となる。Since the composition of the present invention is applied to various substrates because of the above-mentioned characteristics, it can be applied to a region where it could not be used conventionally.
Claims (4)
（Ｂ）で表される化合物、および溶剤を含有する組成物
であり、式（Ａ）で表される化合物および式（Ｂ）で表
される化合物の合計量が組成物全量に対して０．１〜３
０重量％であることを特徴とする撥水防汚性組成物。 【化１】 Ｒｆ1 ：エーテル性の酸素原子を含んでいてもよいパー
フルオロアルキル基、を含有する有機基を示す。 Ｒ1 ：水素原子または炭素数１〜１６の有機基を示す。 ａ：１または２。 ｂ：０または１。ただし、１≦ａ＋ｂ≦２である。 Ｒｆ2 、Ｒｆ3 ：独立に、エーテル性の酸素原子を含ん
でいてもよいパーフルオロアルキル基、を含有する有機
基を示す。 Ｒ2 、Ｒ3 ：独立に、水素原子または炭素数１〜１６の
有機基を示す。 ｃ、ｄ：独立に、０、１または２であって０≦ｃ＋ｄ≦
２である。 ｅ、ｇ：独立に、０、１または２であって０≦ｅ＋ｇ≦
２である。 Ｙ：２価の有機基（ただし、ｃ＋ｅ＝０の場合には、エ
ーテル性の酸素原子を含んでいてもよいパーフルオロア
ルキレン基、を含有する２価の有機基）を示す。1. A compound represented by the following formula (A), a compound represented by the following formula (B), and a composition containing the solvent
And a compound represented by the formula (A) and a compound represented by the formula (B)
The total amount of the compound to be used is 0.1 to 3 relative to the total amount of the composition.
A water-repellent and antifouling composition, which is 0% by weight . Embedded image Rf 1 represents an organic group containing a perfluoroalkyl group which may contain an etheric oxygen atom. R 1 represents a hydrogen atom or an organic group having 1 to 16 carbon atoms. a: 1 or 2. b: 0 or 1. However, 1 ≦ a + b ≦ 2. Rf 2 and Rf 3 each independently represent an organic group containing a perfluoroalkyl group which may contain an etheric oxygen atom. R 2 and R 3 independently represent a hydrogen atom or an organic group having 1 to 16 carbon atoms. c, d: independently , 0 , 1 or 2 and 0 ≦ c + d ≦
2. e, g: independently 0 , 1 or 2 and 0 ≦ e + g ≦
2. Y: a divalent organic group (however, in the case of c + e = 0, a divalent organic group containing a perfluoroalkylene group which may contain an etheric oxygen atom).
求項１記載の撥水防汚性組成物。 （Ｃ） （Ｒ 3 ） h （Ｒ 4 ） i Ｓｉ（ＮＣＯ） 4-h-i Ｒ 3 、Ｒ 4 ：独立に、水素原子または炭素数１〜１６の
有機基。 ｈ、ｉ：独立に、０、１、または２。ただし、
０≦ｈ＋ｉ≦３である。 (2)An agent containing a compound represented by the following formula (C):
The water-repellent and antifouling composition according to claim 1. (C) (R Three ) h (R Four ) i Si (NCO) 4-hi R Three , R Four : Independently a hydrogen atom or a group having 1 to 16 carbon atoms
Organic groups. h, i: 0, 1, or 2 independently. However,
0 ≦ h + i ≦ 3.
を基材表面に処理し乾燥させて得られる撥水防汚性基
材。 3. The water-repellent and antifouling composition according to claim 1 or 2.
Water-repellent antifouling group obtained by treating and drying
Wood.
を基材表面に処理し乾燥させることを特徴とする表面処
理方法。 4. The water-repellent and antifouling composition according to claim 1 or 2.
Surface treatment characterized by treating and drying the surface of the base material
Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8294108A JP2800807B2 (en) | 1996-11-06 | 1996-11-06 | Water repellent / soil repellent composition, water repellent / soil repellent substrate, and method of treating the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8294108A JP2800807B2 (en) | 1996-11-06 | 1996-11-06 | Water repellent / soil repellent composition, water repellent / soil repellent substrate, and method of treating the composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8166406A Division JP2800786B2 (en) | 1996-06-26 | 1996-06-26 | Composition exhibiting water repellency and antifouling property at ordinary temperature, water repellent and antifouling substrate, and treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09165571A JPH09165571A (en) | 1997-06-24 |
| JP2800807B2 true JP2800807B2 (en) | 1998-09-21 |
Family
ID=17803400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8294108A Expired - Fee Related JP2800807B2 (en) | 1996-11-06 | 1996-11-06 | Water repellent / soil repellent composition, water repellent / soil repellent substrate, and method of treating the composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2800807B2 (en) |
-
1996
- 1996-11-06 JP JP8294108A patent/JP2800807B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09165571A (en) | 1997-06-24 |
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